TWI787371B - Sealing material composition, sealing material and electronic substrate - Google Patents

Abstract

The present invention provides a soft and shapeable sealing material composition and sealing material without heating after covering electronic components and the like.

The sealing material composition of the present invention contains: a reaction product of an epoxy compound having two or more epoxy groups and a polyamine; A liquid diene rubber, a reaction product with an epoxy compound having two or more epoxy groups; and a photopolymerization initiator, and has shape-setting properties. The sealing material of the present invention is a photocurable body of the sealing material composition.

Description

Sealing material composition, sealing material and electronic substrate

The present invention relates to a sealing material composition and a sealing material that are pasted on electronic components such as electronic substrates or exposed parts of the metal to protect the adherends such as electronic components from being affected by moisture and foreign matter, and electronic components using the same. substrate.

Sealing materials made of epoxy resins have been known for a long time. This sealing material is used for covering and protecting electronic components and the like after coating and curing a liquid sealing material composition before the epoxy resin is cured on a substrate or the like. The sealing material in the form of hardening the liquid has the advantage that it is easy to flow into the gap of the electronic component because it is liquid, so that it can reliably cover the electronic component. A problem that makes the exposed part also covered. In addition, the liquid sealing material composition may be poor in handling properties, such as the possibility of foreign matter easily adhering to other members before hardening, and the possibility of staining due to adhering to other members. To solve this problem, a solid sheet-shaped sealing material composition has been developed. For example, Japanese Patent Application Laid-Open No. 2012-087292 (Patent Document 1) and the like describe the related sheet-shaped sealing material composition. In addition, JP-A-2015-196783 (Patent Document 2) describes a technology related to a photocurable sheet-shaped sealing material. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2012-087292 [Patent Document 2] Japanese Patent Laid-Open No. 2015-196783

However, according to the technology described in Japanese Patent Laid-Open No. 2012-087292 (Patent Document 1), in order to bury the unevenness of the electronic components and the like on the substrate, it is necessary to heat and soften the sheet-shaped sealing material composition. Heating requires a predetermined time, and there is a problem that it takes time to manufacture the product. Also, since the viscosity of the sealing material composition changes with temperature, if the heating is not sufficient, the softening of the sealing material composition will be insufficient, and there is a possibility that unevenness cannot be buried sufficiently. On the other hand, if the viscosity becomes low due to excessive heating, there is a possibility that the fluid will flow out of the predetermined range. Also, it may not be applicable to low heat-resistant electronic components.

Furthermore, although the light-curable sealing material composition described in Japanese Patent Application Laid-Open No. 2015-196783 is in the form of a sheet, it is still a hard composition, so if it is directly attached to electronic components, etc., there will be problems due to application. Possibility of breakage due to excessive pressure. Therefore, it is necessary to apply heating when making the sealing material composition closely adhere to the unevenness, and there is a problem similar to Patent Document 1.

Therefore, the present invention has been made to solve the above-mentioned problems. That is, an object is to provide a sealing material composition and a sealing material that do not require heating after coating an electronic component or the like, are flexible, and have settability.

In order to achieve the above objects, the sealing material composition of the present invention has the following constitution. That is, the sealing material composition of the present invention has shape fixability, and contains: a reaction product of an epoxy compound having two or more epoxy groups and a polyamine; A reaction product of (meth)acryl-based liquid diene rubber and an epoxy compound having two or more epoxy groups; and a photopolymerization initiator.

Because the sealing material composition of the present invention has shape-setting properties, and contains: the reaction product of an epoxy compound with more than two epoxy groups and a polyamine; base) acryl-based liquid diene rubber, a reaction product with an epoxy compound having two or more epoxy groups; and a photopolymerization initiator, thus becoming Sealant composition for imparting shape fixability and flexibility to epoxy compound, reaction product with polyamine, and reaction product of epoxy compound having two or more epoxy groups and liquid diene rubber above . Therefore, when the sealing material composition of the present invention is pasted on a substrate with concavo-convexities, it can be tightly bonded by pressing with a small load, and it can be easily bonded to the concave portion. In addition, the so-called "formability" refers to the property of maintaining a shape when a predetermined operation or an external force is applied.

In addition, when the sealing material composition of this invention is irradiated with light, it can harden by photopolymerization. Therefore, the sealing material composition can be hardened into a sealing material without heating, and can seal adherends such as electronic components. Also, because the molecular weight of the liquid diene rubber is large, and a part of it forms a reaction product with an epoxy compound or polyamine having two or more epoxy groups, and becomes a matrix for holding an unreacted product, Therefore, the problem of leakage of liquid components is less likely to occur. In addition, the liquid diene-based rubber imparts flexibility, and the sealing material composition and the sealing material which is a light-cured product thereof also have flexibility.

The above-mentioned sealing material composition of the present invention, wherein, the above-mentioned epoxy group is a reactive group carboxyl group; it includes shape-setting properties, and contains: an epoxy compound having two or more epoxy groups, and a polyamine formed by the reaction of Products; reaction products of liquid diene rubber with (meth)acryl and carboxyl groups, and epoxy compounds with more than 2 epoxy groups; products with (meth)acryl and carboxyl groups liquid diene rubber, A reaction product with a polyamine; and a photopolymerization initiator.

In the sealing material composition of the present invention, wherein the above-mentioned epoxy group is a reactive group carboxyl group, it is composed of: a reaction product of an epoxy compound with more than 2 epoxy groups and a polyamine; ) reaction product of liquid diene rubber with acryl group and carboxyl group, and epoxy compound with two or more epoxy groups; and liquid diene rubber with (meth)acryl group and carboxyl group A reaction product with polyamines that imparts setability and flexibility. Therefore, when the sealing material composition of the present invention is pasted on a substrate with concavities and convexities, it can be tightly bonded by pressing with a small load, and can be easily bonded to the concave portion.

The mixture of the above-mentioned liquid composition of the present invention contains: an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene having a reactive group to epoxy groups and a (meth)acryl group Department of rubber, and photopolymerization initiator. Because the formation contains: epoxy compounds with more than two epoxy groups, polyamines, liquid diene rubber with reactive groups to epoxy groups and (meth)acryl groups, and photopolymerization initiators A mixture of liquid compositions, thus forming: an epoxy compound with two or more epoxy groups, a reaction product with a polyamine, an epoxy compound with two or more epoxy groups and a liquid diene system The reaction product of rubber, and the reaction product of polyamine and liquid diene rubber, through covalent bonds, ionic interactions, and other intermolecular interactions, such as gel or rubber polymer composition. Therefore, formability and flexibility can be imparted, and when sticking to a substrate with unevenness, it becomes a sealing material composition that can be tightly bonded by pressing with a small load, and can be easily bonded to a concave portion.

The sealing material composition can be configured such that the above-mentioned liquid composition contains 100 to 2000 parts by mass of the above-mentioned liquid diene rubber with respect to a total of 100 parts by mass of the above-mentioned epoxy compound having two or more epoxy groups and the above-mentioned polyamine. . Since the above-mentioned liquid composition contains 100 to 2000 parts by mass of the above-mentioned liquid diene rubber with respect to the total of 100 parts by mass of the above-mentioned epoxy compound having two or more epoxy groups and the above-mentioned polyamine, it can achieve excellent settability. sealant composition.

The present invention can also constitute a reaction product comprising: an epoxy compound having two or more epoxy groups, and a liquid diene rubber having a reactive group to epoxy groups and a (meth)acryl group; And the photopolymerization initiator, but does not contain the reaction product of polyamine, including fixability.

Because the above-mentioned present invention constitutes a reaction product comprising: an epoxy compound having two or more epoxy groups, and a liquid diene rubber having a reactive group to epoxy groups and a (meth)acryl group; and The photopolymerization initiator, but does not contain the reaction product of polyamine, including the reaction product of the epoxy compound with two or more epoxy groups, and the above-mentioned liquid diene rubber, which has settability, by Covalent bonds, ionic interactions, and other intermolecular interactions form gel-like or rubber-like polymer compositions. Therefore, by imparting shapeability and flexibility, it becomes a sealing material composition that can be adhered to a concave-convex substrate easily by pressing with a small load when it is pasted on a substrate with unevenness.

The above-mentioned present invention can be set as a sealing material composition having a carboxyl group reactive to the above-mentioned epoxy group. Because the above-mentioned present invention is composed of: a reaction product of an epoxy compound having two or more epoxy groups, and a liquid diene rubber having a (meth)acryl group and a carboxyl group; and a photopolymerization initiator, However, it does not contain the reaction product of polyamine, and includes shape-setting properties, so it becomes the product of the above-mentioned epoxy compound having two or more epoxy groups and the reaction product of the above-mentioned liquid diene rubber that imparts shape-setting and flexibility. Sealant composition. Therefore, when the sealing material composition of the present invention is pasted on a substrate with concavities and convexities, it can be tightly bonded by pressing with a small load, and can be easily bonded to the concave portion.

In addition, the above-mentioned present invention can be cured by photopolymerization when irradiated with light. Therefore, the sealing material composition of the present invention can harden the sealing material composition into a sealing material without heating, and can seal adherends such as electronic components. In addition, because the liquid diene rubber has a large molecular weight, and a part of it forms a reaction product with an epoxy compound having two or more epoxy groups, and becomes a matrix for maintaining an unreacted product, it is difficult to produce a liquid diene rubber. Problems with bleed-out of ingredients. Also, the liquid diene rubber imparts Softness makes the sealing material composition and the sealing material of its light-hardened product also soft.

The mixture of the above-mentioned liquid composition of the present invention contains: an epoxy compound with more than two epoxy groups, a liquid diene rubber with a reactive group to epoxy groups and a (meth)acryl group, and a photopolymerization initiator, but does not contain polyamines. Because the composition contains: an epoxy compound with two or more epoxy groups, a liquid diene rubber with a reactive group to epoxy groups and a (meth)acryl group, and a photopolymerization initiator, but not A mixture of liquid compositions containing polyamines, thus forming an epoxy compound with two or more epoxy groups, and the reaction product of the above-mentioned liquid diene rubber, which becomes a gel-like or rubber-like high molecular composition. Therefore, it can be a sealing material composition that imparts shapeability and flexibility, and can be easily adhered to a concave portion by pressing with a small load when sticking to a substrate with unevenness.

The sealant composition may be configured such that the liquid composition contains 100 to 2600 parts by mass of the liquid diene rubber relative to 100 parts by mass of the epoxy compound having two or more epoxy groups. Since the liquid composition contains 100 to 2600 parts by mass of the liquid diene rubber with respect to 100 parts by mass of the epoxy compound having two or more epoxy groups, it can be a sealing material composition excellent in shape fixability.

The sealing material composition may constitute the above-mentioned liquid composition system further containing an epoxy resin curing agent other than polyamine. Since the above-mentioned liquid composition further contains an epoxy resin curing agent other than a polyamine, the low moisture permeability and water resistance of the sealing material can be improved.

The above-mentioned sealing material composition of the present invention may further contain: a liquid diene rubber that does not have a (meth)acryl group but has a reactive group to an epoxy group. Because the above-mentioned present invention further contains: a liquid diene rubber that does not have a (meth)acryl group but has a reactive group to an epoxy group, it is easy to handle, and the maximum tensile stress is increased. Not prone to breakage. Therefore, the trackability of the covered electronic components can be improved, the unevenness of the electronic components can be buried or along the surface of the electronic components with a low load, and defects are less likely to occur during elongation. In addition, by reducing the crosslinking density derived from (meth)acryl groups, the stretchability after hardening can be improved, and it can become a better sealing material for flexible substrates and elongated substrates.

In the sealing material composition of the present invention described above, the liquid diene rubber having a reactive group to an epoxy group and a (meth)acryl group has a (meth)acryl group but does not have a A mixture of a first liquid diene rubber having reactive groups to epoxy groups; and a second liquid diene rubber having reactive groups to epoxy groups but not having (meth)acryl groups. Because the above-mentioned present invention is a liquid diene rubber having a reactive group to an epoxy group and a (meth)acryl group, it has a (meth)acryl group but does not have a reactive group to an epoxy group. A mixture of the first liquid diene rubber with epoxy group and the second liquid diene rubber with no (meth)acryl group, which is reactive to epoxy group, so it can be used in one molecule Liquid diene-based rubber that does not contain reactive groups such as epoxy groups and di-reactive groups such as (meth)acryl groups.

The above-mentioned sealing material composition of the present invention contains: a reaction product of a liquid diene rubber having a (meth)acryl group and a carboxyl group, and a polyamine; and a photopolymerization initiator, but does not contain 2 Reaction products of epoxy compounds with more than one epoxy group, including shape-defining properties.

The above-mentioned present invention contains: a liquid diene rubber having a (meth)acryl group and a carboxyl group, a reaction product with a polyamine; and a photopolymerization initiator, but does not contain a rubber having two or more epoxy groups. The reaction product of the epoxy compound includes shape fixability, so it is a sealant composition that is endowed with shape fixity and flexibility by the reaction product of the above-mentioned polyamine and the above-mentioned liquid diene rubber. Therefore, when the sealing material composition of the present invention is pasted on a substrate with concavities and convexities, it can be tightly bonded by pressing with a small load, and can be easily bonded to the concave portion.

In addition, when the sealing material composition of the present invention is irradiated with light, it can be cured by photopolymerization. Therefore, without heating, the sealing material composition can be hardened to form a sealing material, which can seal adherends such as electronic components. In addition, the liquid diene rubber has a relatively high molecular weight, and a part of it forms a reaction product with polyamines, which serves as a matrix for holding unreacted products, so the problem of bleeding of liquid components is less likely to occur. In addition, the liquid diene-based rubber imparts flexibility, and the sealing material composition and the sealing material which is a light-cured product thereof also have flexibility.

The sealing material composition of the present invention described above can be composed of polyamine, liquid diene rubber with (meth)acryl and carboxyl groups, and a photopolymerization initiator, but does not contain more than two rings. Mixture of liquid compositions of oxy-epoxy compounds. Because the composition contains: polyamine, liquid diene rubber with (meth)acryl group and carboxyl group, and photopolymerization initiator, but does not contain liquid combination of epoxy compound with more than 2 epoxy groups A mixture of substances, thus forming a reaction product of polyamine and liquid diene rubber, which becomes a polymer composition forming a gel or rubber. Therefore, it can become a sealing material composition that provides shapeability and flexibility, and can be tightly bonded by pressing with a small load when it is pasted on a substrate with unevenness, and can be easily bonded to a concave portion.

The sealing material composition may be configured such that the liquid composition contains 100 to 2000 parts by mass of the liquid diene rubber relative to 100 parts by mass of the polyamine. Since the liquid composition contains 100 to 2,000 parts by mass of the liquid diene rubber relative to 100 parts by mass of the polyamine in total, it can be a sealing material composition excellent in shape fixability.

Furthermore, the sealing material is composed of a photocurable body of any one of the above-mentioned sealing material compositions. Since the sealing material is a light-hardening body of any of the above-mentioned sealing material compositions, the sealing material also has flexibility, including proper adhesiveness. Therefore, the sealing material of the present invention has excellent airtightness and excellent sealing effect on the adherend. In other words, since the sealing material composition is soft, it is only necessary to form the sheet-shaped sealing material composition to be pressed and bonded to the sealed electronic components to bury the unevenness of the electronic components. Moreover, even when covering a relatively large electronic component, the sealing material composition can adhere|attach closely along the surface of an electronic component while elongating, and can cover an electronic component.

Furthermore, the storage elastic modulus of the sealing material is 0.7~5.4MPa. Because the storage elastic modulus is 0.7~5.4MPa, it can be a sealing material with high strength and excellent flexibility.

In the above-mentioned electronic substrate of the present invention, electronic components are sealed with any one of the above-mentioned sealing materials. The electronic substrate of the present invention is an electronic substrate that properly protects the electronic components from moisture, foreign matter, etc., because the electronic components are sealed with any of the above-mentioned sealing materials.

In the above-mentioned electronic substrate of the present invention, the height T ₂ of the electronic component relative to the thickness T ₁ of the sealing material is T ₁ > T ₂ , and the surface of the sealing material embedding the unevenness of the electronic component is slightly smooth. In the electronic substrate of the present invention, the height T ₂ of the electronic component is T ₁ > T ₂ relative to the thickness T ₁ of the sealing material, and the surface of the sealing material embedding the unevenness of the electronic component is slightly smooth, so even if there are multiple electronic components with different heights, The electronic substrate of the component can still be covered with a sealing material to form a slightly smooth plane. Therefore, not only can the electronic components be sealed from the outside air, but also can be stably maintained.

In the above-mentioned electronic substrate of the present invention, the height T ₂ of the electronic component is set to T ₁ ≦ T ₂ with respect to the thickness T ₁ of the sealing material, and the sealing material is in close contact with the outer surface of the electronic component. In the present invention described above, the height T ₂ of the electronic component is set to T ₁ ≦ T ₂ with respect to the thickness T ₁ of the sealing material, and the sealing material is in close contact with the outer surface of the electronic component, so even if the electronic substrate has a plurality of electronic components with different heights, Still, at least the sides can be covered by the sealant. Therefore, the side surfaces of the electronic components can be sealed and held stably.

The above-mentioned electronic substrate of the present invention includes a flexible base material with a storage elastic modulus of 0.7-50 MPa. Because the above-mentioned electronic substrate of the present invention includes a flexible base material with a storage elastic modulus of 0.7-50 MPa, the sealing material can be prevented from being excessively stretched by laminating the above-mentioned sealing material with the flexible base material, so that the sealing Electronic substrates whose materials are not easily damaged.

According to the sealing material composition and sealing material of the present invention, they have shape fixability and flexibility, and are excellent in handling properties. Also, according to the electronic substrate of the present invention, it is possible to appropriately protect electronic components from moisture, foreign substances, and the like.

The sealing material composition and the sealing material of the hardened|cured body of this invention are demonstrated in detail based on embodiment. Repeated descriptions of materials, materials, manufacturing methods, effects, functions, etc. that are repeated in the respective embodiments will be omitted.

＜Sealing Material Composition＞

The sealing material composition of the present invention is pasted on an electronic substrate (also referred to as "substrate") on which electronic components are arranged, and after being crimped to cover the electronic components and closely bonded, it is irradiated with light to harden to become a sealing material, which improves the resistance to heat. The adhesiveness of electronic components protects electronic components from moisture and foreign matter.

(1) The first embodiment:

The sealing material composition of the first embodiment is based on: an epoxy compound having two or more epoxy groups, a polyamine, a liquid diene having a reactive group to an epoxy group and a (meth)acryl group. It is a gel-like composition or a rubber-like composition obtained by heating a liquid mixture of rubber and a photopolymerization initiator as essential components. Hereinafter, it demonstrates from these components.

Liquid diene rubber with epoxy-reactive groups and (meth)acryl groups:

Liquid diene rubber with epoxy-reactive groups and (meth)acryl groups (hereinafter also referred to as "liquid diene rubber") is a light-curing component contained in the sealing material composition , A component that imparts rubber elasticity (softness), low moisture permeability, water resistance, and adhesiveness to an adherend to the sealing material. Moreover, it has the effect of improving the mechanical strength of a sealing material, and improving the stretchability of a sealing material.

Liquid diene-based rubber with epoxy-reactive groups and (meth)acryl groups not only has both epoxy-reactive groups and (meth)acryl groups in a single molecule In this case, it can also be formed: liquid diene rubber with reactive groups to epoxy groups but no (meth)acryl groups, and liquid diene rubbers with (meth)acryl groups but no epoxy groups A mixture of liquid diene rubbers with reactive groups. Therefore, the above-mentioned liquid diene rubber system only needs to have epoxy-reactive groups and (meth)acryl groups in the liquid diene rubber in the mixture.

Liquid diene-based rubber is liquid at room temperature. In the sealant composition, part of it forms a reaction product with an epoxy compound or polyamine having two or more epoxy groups, and the unreacted liquid di The ethylenic rubber is held by the reaction product and a matrix that is a hardened epoxy resin.

The viscosity of liquid diene rubber is preferably 1~1000Pa‧s. If it is less than 1Pa‧s, the cross-linked structure will form a three-dimensional overdense, which may cause the hardened sealing material to become brittle. On the other hand, if it is more than 1000 Pa‧s, the adhesive force to the adherend may decrease.

The number of (meth)acryl groups contained in one molecule of the liquid diene rubber is preferably 2-3. When the number of functional groups is 1, the crosslinked structure is not developed, which may lead to a decrease in the strength of the sealing material. On the other hand, when the number of functional groups is 4 or more, the three-dimensional formula is too dense due to the crosslinked structure, and thus the sealing material may become brittle.

Reactive groups to epoxy groups can be exemplified such as: acid anhydride group, carboxyl group, hydroxyl group, amine group, imide group, imidazole group, mercapto group, but only those with moderate reactivity with epoxy group and good material availability From a viewpoint, carboxyl groups and acid anhydride groups are preferred.

When the liquid diene rubber is cured alone, the storage elastic modulus E' is preferably a component of 0.01 to 10 MPa. When the storage elastic modulus is 0.01 MPa or less, the strength and toughness of the sealing material become extremely weak, and there is a possibility that the sealing object cannot be sufficiently protected. When the storage elastic modulus is 10 MPa or more, the sealing material may harden more than necessary.

In addition, specific examples of the liquid diene rubber include liquid polyisoprene, liquid polybutadiene, and liquid polyisobutylene.

Epoxy compounds with more than 2 epoxy groups:

The sealing material composition of the first embodiment is formed with an epoxy compound having two or more epoxy groups as an essential raw material, and the sealing material composition mainly contains: an epoxy compound having two or more epoxy groups A reaction product with liquid diene rubber, and a reaction product of an epoxy compound having two or more epoxy groups and a polyamine. In addition, when a curing agent for an epoxy resin described later is further included, an epoxy resin cured product that reacts with an epoxy compound having two or more epoxy groups and a curing agent for an epoxy resin may be included. An epoxy component having unreacted epoxy groups may also be contained.

The epoxy compound system which has 2 or more epoxy groups can use the epoxy monomer and oligomer which have 2 or more epoxy groups in 1 molecule. Also, if some of the molecules used contain soft skeletons such as polyethylene glycol skeleton, polypropylene glycol skeleton, polyether skeleton, urethane skeleton, polybutadiene skeleton, nitrile rubber skeleton, etc., the hardness of the sealing material composition can be increased. It is softer, so it is better.

Specific examples of the above-mentioned epoxy compounds with more than two epoxy groups are: bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol‧novolac type epoxy resin, cresol‧novolac type epoxy resin , glycidylamine epoxy resin, naphthalene epoxy resin, triphenol alkane epoxy resin, biphenyl epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc.

Furthermore, the epoxy resin system with a soft skeleton can be exemplified by reacting aromatic dihydroxy compounds such as bisphenol A with alkylene oxides such as ethylene oxide and propylene oxide to synthesize polyalkylene resins. Compounds with a diol skeleton, and then further epoxidized the end of the compound with a polyalkylene glycol skeleton, and the obtained "aromatic dihydroxy compound and polyalkylene glycol are bonded, with an epoxy group at the end Epoxy compounds such as propylene glycol and butanediol or polyalkylene glycols such as diethylene glycol and polypropylene glycol are epoxidized, and further reacted with aromatic dihydroxy compounds such as bisphenol A, Then epoxidize the product to obtain "an epoxy compound that is bonded to an alkanediol or polyalkylene glycol and an aromatic dihydroxy compound and has an epoxy group at the end"; aliphatic and aromatic hydrocarbon compounds , propylene glycol, butanediol and other alkanediols, or polyalkylene glycols such as diethylene glycol and polypropylene glycol, carry out divinyl etherification, and further react with aromatic dihydroxy compounds such as bisphenol A, and then generate "An epoxy compound with an epoxy group at the end that is bonded to an aliphatic skeleton, an aromatic skeleton, or an alkane diol, polyalkylene glycol, and an aromatic dihydroxy compound" obtained by epoxidizing a substance; Aliphatic dicarboxylic acids such as dimer acid or sebacic acid react with bisphenol A epoxy resin and other epoxides to obtain "epoxy compounds with aliphatic skeleton"; polyalkylene oxides such as propylene oxide "An epoxy compound having a polyalkylene glycol structure with an epoxy group at the end" obtained by epoxidizing the end of a diol.

Among them, from the viewpoint of improving the softness and brittleness after hardening, it is preferable to use an aliphatic skeleton, an aromatic skeleton, or an alkanediol or polyalkylene glycol, and an aromatic dihydroxy compound. Bonding, an epoxy compound with an epoxy group at the end.

These epoxy compounds having two or more epoxy groups may be used alone or in combination of two or more. In addition, the epoxy compound having two or more epoxy groups may be liquid or solid at normal temperature. In addition, the case of "normal temperature" in this invention means the state of 25 degreeC.

Polyamine:

The sealing material composition of the first embodiment is formed using polyamine as an essential raw material, and the sealing material composition mainly contains: a reaction product of polyamine and liquid diene rubber; The reaction product of the epoxy compound of the above epoxy group. In addition, polyamines are general hardeners for epoxy compounds with more than two epoxy groups, and are also contained in epoxy compounds that react with epoxy compounds with more than two epoxy groups and polyamines. In the skeleton of the resin hardened body. Unreacted polyamine components may also be contained.

In the present invention, "polyamine" refers to a compound having at least a molecular weight exceeding 100 and containing two or more amino groups. For example: aliphatic polyamines, polyether polyamines, alicyclic amines, aromatic amines, polyamidoamines, amine adducts, etc.

The polyamine system can be liquid or solid, because it contains an epoxy compound with two or more epoxy groups that is an essential component of the sealing material composition, so it is best to use the so-called latent hardener and the so-called polyamine better. The reason is that if a latent hardener is used, it will not harden immediately after mixing, so it can suppress the increase in viscosity when mixing an epoxy compound having two or more epoxy groups and a liquid diene rubber. The sealing material hardened by the sealing material composition protects the sticky body from the influence of water and water vapor. Therefore, if there are air bubbles in the sealing material, the properties of the sealing material will be deteriorated. Therefore, air bubbles need to be removed during the manufacturing process of the sealing material composition, but if the viscosity of the raw materials rises sharply immediately after mixing, it may be difficult to remove the air bubbles. However, if the increase in viscosity during manufacturing can be suppressed, the air bubbles in the sealing material can also be reliably degassed. Therefore, if a latent hardener is used, the deterioration of properties caused by air bubbles can be prevented.

An example of the above-mentioned latent curing agent can be exemplified: it is solid at normal temperature, but has the property of being activated when melted at a predetermined temperature. Among the above-mentioned polyamines, aromatic amines and amine adducts activated at 60°C to 120°C are preferred.

Examples of aliphatic amines include hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis(hexamethylene) Triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetrakis(hydroxyethyl)ethylenediamine, and the like.

Examples of polyether polyamines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Alicyclic amines can be exemplified for example: isophorone diamine, condensed tetraphenyl diamine, N-aminoethylpiperidine, bis(4-amino-3-methyldicyclohexyl)methane, bis (Aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)2,4,8,10-tetraspiro(5,5)undecane, nor-alkenediamine, etc.

Examples of aromatic amines include tetrachloro-p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4 -Diaminoanisole, 2,4-toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2 -diphenylethane, 2,4-diaminodiphenylamine, 4,4'-diaminodiphenylamine, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-(diaminobenzylamine, Methylaminomethyl)phenol, triethanolamine, methylbenzylamine, α-(m-aminophenyl)ethylamine, α-(p-aminophenyl)ethylamine, diaminodiethyldimethyldi Benzene, α,α'-bis(4-aminophenyl)-p-diisopropylbenzene, etc.

Among the above specific examples, aliphatic amines, polyether polyamines, and alicyclic amines are preferably used in consideration of compatibility with other raw materials and flexibility of sealing materials.

The total content of the epoxy compound having two or more epoxy groups and the polyamine is preferably 5 to 50% by mass in the sealing material composition and sealing material. If it is 5 mass % or less, there exists a possibility that a sealing material composition may not have predetermined shapeability. On the other hand, if it is 50% by mass or more, the sealing material may be too hard. Also, since the content of the liquid diene rubber which is a photocurable component is relatively reduced, there is a possibility that the adhesiveness may be lowered. In addition, when the curing agent for the epoxy resin described below is further included as an optional component, the total content including the epoxy resin curing agent, in addition to the epoxy compound having two or more epoxy groups and the polyamine, is In the sealing material composition and sealing material, it is preferable to contain 5-50 mass %. The reason is the same as above.

Furthermore, with respect to a total of 100 parts by mass of the epoxy compound having two or more epoxy groups and the polyamine, the blending amount of the liquid diene rubber is preferably 100 to 2000 parts by mass, and 400 to 1600 parts by mass. Quality parts are better. When the liquid diene rubber is 100% by mass or less, the sealing material composition and the sealing material may become hard. And there is a possibility that the adhesiveness of a sealing material may fall. On the other hand, if the amount of the liquid diene rubber is 2000 parts by mass or more, the settability of the sealing material composition may be impaired, and handling may be impaired, such as difficulty in pasting.

Reaction product of epoxy compound with two or more epoxy groups and liquid diene rubber, reaction product of epoxy compound with two or more epoxy groups and polyamine:

As mentioned above, the sealing material composition contains the reaction product of the epoxy compound which has 2 or more epoxy groups, and a liquid diene rubber. Specifically, the reaction product is produced by reacting epoxy group-reactive groups included in the liquid diene rubber. In addition, it also includes a reaction product of an epoxy compound having two or more epoxy groups and a polyamine. In addition, if the liquid diene rubber has a carboxyl group reactive to the epoxy group, it also contains polyamines, and the reaction of the liquid diene rubber with (meth)acryl and carboxyl groups. product.

Reaction products of epoxy compounds having two or more epoxy groups and liquid diene rubber, reaction products of polyamines and liquid diene rubber, and epoxy compounds having two or more epoxy groups and The reaction product of the polyamine forms a covalent bond, ionic interaction, or other interaction. That is, the liquid diene rubber itself is liquid, and if it is contained in a large amount, it may impair the settability of the sealing material composition, and the content of the liquid diene rubber can be reduced by forming a reaction product. Amount, and increase the reactive product that maintains it, it is judged that the sealing material composition will impart shapeability and maintain appropriate softness.

Furthermore, these reaction products are relatively high in viscosity or solid in comparison with the components before the reaction. Therefore, specifically, the tensile elongation at break is significantly improved, and when the sealing material composition is stretched, it is less likely to be pulverized. Therefore, when the flat sealing material composition is pasted on a sealing object with unevenness, the part extending along the unevenness is not easy to break, which can suppress the occurrence of adverse conditions caused by the fracture of the sealing material. In other words, this phenomenon can be applied to larger unevenness. The sealed object.

If the reaction products are viewed individually, when the reaction products of epoxy compounds with more than two epoxy groups and liquid diene rubber are included, the temperature characteristics of the relevant dynamic viscoelasticity measurement will become the storage elastic modulus. A heat-resistant sealing material composition with small temperature change and excellent settability. On the other hand, when the reaction product of polyamine and liquid diene rubber has settability, it becomes excellent thermoplasticity in which the storage elastic modulus measured by the dynamic viscoelasticity measurement decreases significantly as the temperature increases. If the temperature is increased, the sealing material composition with increased flexibility can be obtained. This kind of sealing material composition is that when the object to be adhered has fine unevenness, the sealing material composition can be tightly adhered to the corners of the unevenness by auxiliary heating. However, the two features can be adjusted by changing the ratio of the epoxy compound having two or more epoxy groups and the polyamine.

In addition, when the (meth)acryl group of the liquid diene rubber reacts with the amine group of the polyamine to form a reaction product, if all the (meth)acryl groups participate in the reaction, there will be The possibility of loss of the photoreactivity of the sealing material composition, but after intensive research by the inventors, it was confirmed that even if an excessive amount of polyamine was added, unreacted (meth)acryl groups could still remain, and it would not be found The photocuring failure of the sealing material composition may occur due to the formation of the reaction product of the polyamine and the liquid diene rubber.

Photoradical polymerization initiator:

系、苯乙酮系、醯化膦系等光聚合起始劑。光自由基聚合起始劑的摻合量，相對於液狀二烯系橡膠的摻合量100重量份，係以0.1~10重量份為佳、1~8重量份更佳。The photoradical polymerization initiator is one that causes liquid diene rubber to react with light to harden it. Specific systems can be used such as: benzophenone series, oxygen sulfur

series, acetophenone series, phosphine series and other photopolymerization initiators. The blending amount of the photoradical polymerization initiator is preferably 0.1 to 10 parts by weight, more preferably 1 to 8 parts by weight, based on 100 parts by weight of the liquid diene rubber.

Other ingredients:

It may further contain a liquid diene rubber that does not have a (meth)acryl group but has a reactive group to an epoxy group. If it further contains a liquid diene rubber that does not have a (meth)acryl group but has a reactive group to an epoxy group, the handling property of the sealing material composition can be improved, and the maximum tensile stress can be increased , not easy to break due to elongation. Therefore, the trackability of the covered electronic components can be improved, and the unevenness of the electronic components can be buried under a low load, or along the surface of the electronic components, and it is difficult to cause defects due to the elongation of the sealing material. In addition, by reducing the crosslinking density derived from (meth)acryl groups, the stretchability after hardening can be improved, and it can become a better sealing material for flexible substrates and elongated substrates.

An example of an optional component is a hardener that may contain an epoxy resin. In order to distinguish the polyamines that are the above-mentioned essential components from the so-called hardeners for epoxy resins here, when the term "hardeners for epoxy resins" is referred to in this specification and the scope of the patent application, it refers to other than the above-mentioned polyamines, and other than the above-mentioned polyamines. A hardening reaction between epoxy compounds with two or more epoxy groups.

Cured epoxy resin obtained by thermally curing an epoxy compound with two or more epoxy groups and a hardener for epoxy resin, and an epoxy compound with two or more epoxy groups and a liquid diene system The reaction product of rubber, and the reaction product of polyamine and liquid diene rubber are components that impart fixability to the sealant composition and the sealant. In addition, it also contributes to improving the low moisture permeability and water resistance of the sealing material. When the epoxy compound having two or more epoxy groups is an epoxy resin with a soft skeleton, the flexibility of the sealing material composition and the sealing material can be improved.

As the curing agent for epoxy resin, among the commonly used epoxy resin curing agents, those other than the aforementioned polyamines can be used. For example: imidazole-based hardeners, acid anhydride-based hardeners, phenol-based hardeners, polythiol-based hardeners, isocyanates, blocked isocyanates, etc. These epoxy resin curing agents may be used alone or in combination of two or more. In addition, the blending ratio of the epoxy resin hardener to the epoxy compound having two or more epoxy groups can be set to the same blending ratio as when the epoxy resin main agent and the hardener are generally used.

The hardener content of the epoxy resin, as mentioned above, the total content of the epoxy compound with two or more epoxy groups, the polyamine, and the epoxy resin hardener, in the sealing material composition and the sealing material, is 5 ~50% by mass is preferred. If it is 5 mass % or less, there exists a possibility that a sealing material composition may not have predetermined shapeability. On the other hand, if it exceeds 50% by mass, the sealing material may become too hard. Moreover, since the content of the liquid diene rubber which is a photocurable component is relatively reduced, there exists a possibility that adhesiveness may fall.

In addition to the epoxy resin hardener, various additives may be appropriately blended within the range not departing from the gist of the present invention. For example: silane coupling agent, polymerization terminator, defoamer, light stabilizer, antioxidant, antistatic agent, plasticizer such as polyisoprene or polybutadiene, tackifier, hardening accelerator, etc. For example, when the functional group that reacts with the epoxy group is an acid anhydride group, it is preferable to add clay containing a tertiary amine to the above-mentioned hardening accelerator to accelerate the reaction. In addition, various fillers such as insulating fillers such as silica and clay, conductive fillers, soft magnetic fillers, and thermally conductive fillers can also be used to provide functions that match the purpose.

(2) The second embodiment:

The sealing material composition of the second embodiment contains an epoxy compound having two or more epoxy groups, a liquid diene rubber having a reactive group to epoxy groups and a (meth)acryl group, and The photopolymerization initiator is an essential component and does not contain polyamine. The relevant raw materials are the same as those described in the first embodiment. The relevant optional components are also the same as those in the first embodiment, for example, a curing agent for epoxy resin may be included.

The sealing material composition of the second embodiment also mainly contains an epoxy compound having two or more epoxy groups and a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber. By containing such a reaction product, it becomes a heat-resistant sealing material composition excellent in shape fixability. The temperature characteristics of the relevant dynamic viscoelasticity measurement can be obtained more systematically, and it is a sealing material composition with a small temperature change of the storage elastic modulus.

The content of the epoxy compound having two or more epoxy groups is preferably 5 to 50% by mass in the sealing material composition and sealing material. If it is 5 mass % or less, there exists a possibility that a sealing material composition may not have predetermined shapeability. On the other hand, if it is 50% by mass or more, the sealing material may become too hard. Moreover, since the content of the liquid diene rubber which is a photocurable component is relatively reduced, there exists a possibility that adhesiveness may fall. In addition, when the optional component system further contains an epoxy resin curing agent described later, the total content of the epoxy compound having two or more epoxy groups and the epoxy resin curing agent is different between the sealing material composition and the sealing material. Among them, it is preferable to contain 5 to 50% by mass. The reason is the same as above.

Furthermore, with respect to 100 parts by mass of the epoxy compound having two or more epoxy groups, the blending amount of the liquid diene rubber is preferably 100-2600 parts by mass, more preferably 400-1600 parts by mass. When the liquid diene rubber is 100 parts by mass or less, the sealing material composition and the sealing material may become hard. Moreover, there exists a possibility that the adhesiveness of a sealing material may fall. On the other hand, when the amount of the liquid diene rubber exceeds 2600 parts by mass, the settability of the sealing material composition may be impaired, and the handling property may be impaired, such as making the sticking operation difficult.

Since the sealing material composition of this embodiment does not contain polyamine, storage stability can be improved. In addition, because it does not contain crosslinking caused by the reaction of polyamines and epoxy groups, when it is hardened to form a sealing material, the flexibility and stretchability can be improved. Furthermore, the sealing material composition is excellent in handling properties.

(3) The third embodiment:

The sealing material composition of the third embodiment contains polyamine, liquid diene rubber with (meth)acryl group and carboxyl group, and photopolymerization initiator as essential components, and does not contain more than two Epoxy-based epoxy compounds. The relevant raw materials are the same as those described in the first embodiment. The optional component system can be set as the same as the first embodiment, but even if it contains a hardener for epoxy resin, it does not contain epoxy compounds with more than 2 epoxy groups that are the reaction object, so it is difficult to show that it is difficult to show that it is caused by containing epoxy resin Characteristics caused by hardeners.

The polyamine of the sealing material composition of the third embodiment also mainly contains the reaction product of the polyamine and the liquid diene rubber. By containing the reaction product in this way, it becomes a sealing material composition excellent in thermoplasticity. Specifically, it is possible to obtain the temperature characteristics of the related sealing material composition, the storage elastic modulus determined by the dynamic viscoelasticity measurement, and the sealing material composition that obviously decreases as the temperature increases. That is, when the temperature is increased, a sealing material composition having increased flexibility can be obtained. This kind of sealing material composition is that when the object to be adhered has fine unevenness, the sealing material composition can be tightly adhered to the corners of the unevenness by applying auxiliary heating.

The content of the polyamine is preferably 5 to 50% by mass in the sealing material composition and sealing material. If it is 5 mass % or less, there exists a possibility that a sealing material composition may not have predetermined shapeability. On the other hand, if it is 50% by mass or more, the sealing material may be too hard. Moreover, since the content of the liquid diene rubber which is a photocurable component is relatively reduced, there exists a possibility that adhesiveness may fall.

Furthermore, the blending amount of the liquid diene rubber is preferably 100 to 2000 parts by mass, more preferably 400 to 1600 parts by mass, based on 100 parts by mass of the polyamine. When the liquid diene rubber is 100 parts by mass or less, the sealing material composition and the sealing material may become hard. Moreover, there exists a possibility that the adhesiveness of a sealing material may fall. On the other hand, if the amount of the liquid diene rubber is 2000 parts by mass or more, the settability of the sealing material composition may be impaired, and the handling property may be impaired, such as making the sticking operation difficult.

＜Manufacture of sealing material composition＞

When manufacturing any one of the sealing material compositions in the first to third embodiments, a liquid composition (hereinafter referred to as "liquid composition") which is a raw material used in each embodiment is prepared. Then, the liquid composition is heated.

In the case of the sealing material composition of the first embodiment, the reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber is produced, and the epoxy compound having two or more epoxy groups is regenerated. A hardened epoxy resin product of a reaction product of a chemical compound or polyamine. When a curing agent for epoxy resin is further contained, a cured epoxy resin body that is a reaction product of an epoxy compound having two or more epoxy groups and an epoxy resin curing agent is produced. Then, the liquid composition is solidified by these reactions, and the solid sealing material composition is obtained.

In the case of the sealing material composition of the second embodiment, a reaction product of an epoxy compound having two or more epoxy groups and a liquid diene rubber is produced. When a curing agent for epoxy resin is further contained, a cured epoxy resin body that is a reaction product of an epoxy compound having two or more epoxy groups and an epoxy resin curing agent is produced. Then, the liquid composition is solidified by these reactions, and the solid sealing material composition is obtained.

In the case of the sealing material composition of the third embodiment, a reaction product of a polyamine and a liquid diene rubber is produced. Then, the liquid composition is solidified by these reactions, and the solid sealing material composition is obtained.

＜Properties of sealing material composition＞

Any of the sealing material compositions in the first embodiment to the third embodiment has predetermined shape fixability. Therefore, when it is pasted on a sealed object, it can be pasted within the target range without any possibility of flowing out of the predetermined range. In addition, these sealing material compositions can set the 23° C. storage elastic modulus E′ within the range of 0.004-0.75 MPa. By setting the storage elastic modulus E' to 0.004~0.75MPa, it becomes extremely soft, so when the sealing material composition is pressurized and tightly bonded to the electronic substrate, a low load that does not apply excessive stress to the electronic substrate is used , the unevenness of electronic components can be traced softly. Therefore, in a state where no load is applied to the electronic substrate, it can be tightly sealed with the electronic substrate without a gap. If it is less than 0.004MPa, the strength of the sealing material composition is relatively weak, and when it is pasted to a sealing object with unevenness, the part extending along the unevenness may easily break. On the other hand, when it is 0.75 MPa or more, it becomes hard more than necessary, and when affixing a sealing material composition to a sealing object, a large pressure may be required. Also, the storage elastic modulus E' is preferably in the range of 0.01 to 0.60 MPa. The reason is that when the storage elastic modulus E' is 0.01 or more, the sealing material composition is not easily deformed when it is peeled from the release film, and the handling property such as sticking work is excellent. The reason is that if the storage elastic modulus E' is 0.60 or less, the load on the electronic substrate can be minimized. In addition, electronic substrates also include resin substrates, flexible substrates, elongated substrates, and the like.

The sealant composition may or may not have adhesiveness, but preferably has predetermined adhesiveness. The reason is that if the sealant composition has adhesiveness, after the sealant composition is placed on the object to be adhered, there will be no positional displacement due to vibration and impact, and the sticking and sealing operations can be easily performed. Adhesive strength is not strictly necessary, but it is preferable to have adhesiveness to such an extent that the sealing material composition will not be shifted due to vibration and shock when placed behind the object to be adhered. Specifically, it is preferable to have such an adhesiveness that no gap occurs for about 30 seconds after the sealing material composition is adhered to a substrate having a height of 25% of the thickness of the sealing material composition.

More specifically, the thickness of the sealing material composition is preferably 0.2-2.0 mm. If it is 0.2 mm or less, handling of the sealing material composition may be difficult. On the other hand, if it is more than 2.0 mm, ultraviolet rays may not sufficiently penetrate deep into the sealing material composition, resulting in insufficient curing. Also, since the sealing material of the present invention is soft, it is preferable that the thickness of the sealing material composition be set at 0.5-2.0 mm to improve the cushioning effect of protecting electronic components from impact.

It is preferable that the sealing material composition has a certain degree of transparency. Even if the sealing material composition is cloudy to some extent, it can still be cured, but if the transparency is excessively impaired, when the sealing material composition is photocured, the deep curability may be impaired.

＜Manufacture of sealing material＞

Each sealing material of 1st - 3rd embodiment can be manufactured by photocuring the sealing material composition of 1st - 3rd embodiment. More specifically, the sealing material composition is pasted on the electronic components provided on the electronic substrate and the metal-exposed parts, and after covering the adherend such as the electronic components, the liquid diene rubber is irradiated with light. The sealing material can be formed by hardening by photoradical polymerization. At this time, if the sealant composition has adhesive force, the adherend is pressed with a jig or the like so that the sealant is in close contact with the irregularities of the adherend while being crushed. Then, by lifting the jig and irradiating light quickly, the sealing material composition can be cured in a state of being in close contact with the adherend. On the other hand, when the sealing material composition has no adhesive force, the light-transmitting jig is used to make the sealing material closely contact the unevenness of the adherend while being crushed. Then, in this state, by irradiating light through the jig, the sealing material composition can be cured in a state of being in close contact with the adherend. In addition, the light-transmitting jig can use, for example, acrylic resin, glass, sapphire, and other materials that can transmit light of the wavelength used. In addition, the same method as that of the non-adhesive sealing material composition can also be used for the adhesive sealing material composition.

＜Properties of sealing material＞

Any sealing material in the first embodiment to the third embodiment formed by irradiating the sealing material composition of the first embodiment to the third embodiment with light, is a soft rubber-like elastic body, and has a Tracking the softness of flexible substrates. Specifically, the storage elastic modulus E' at 23° C. measured by a dynamic viscoelasticity measuring device can be set within the range of 0.5-10 MPa, preferably 0.7-5.4 MPa. If it is set within this range, even if it is used in a flexible deformation application, there is no possibility of peeling or damage, and the sealing object can be reliably sealed. If the storage elastic modulus E' is less than 0.5MPa, the strength of the sealing material may decrease. On the contrary, if the storage elastic modulus E' is more than 10MPa, it may not be suitable for applications requiring flexibility. . Also, if it is set at 0.7 to 5.4 MPa, it can be a sealing material with high strength and excellent flexibility.

The sealing material has predetermined adhesiveness and waterproof performance meeting IPX7 specified in JIS C0920. Therefore, the sealing object can be surely protected from water. In addition, the water vapor permeability of the sealing material is 50g/m ² ·24h or less. Therefore, even in high-humidity environments, the sealed object is protected from water.

Because the sealing material composition has shapeability and softness, the sealing material composition can easily penetrate into the concave part of the electronic substrate by pressing the sealing material composition against the concave-convex electronic substrate with a small load to make close contact. In addition, since the sealing material has a small storage modulus of elasticity and is soft, even if it is hardened while embedding the unevenness of the electronic substrate, residual stress does not easily remain, and the electronic element can be stably sealed over a long period of time.

For example, the conventional sheet-shaped sealing material that is not rubber-like, but softened or melted by heating, will elongate according to the softened or melted state even if it lacks rubber elasticity, especially when trying to trace the surface of a high-level electronic component, it will be crushed In contrast, the sealing material composition of the present invention can reach an elongation of about 400% in most cases, is not easily crushed, and can easily cover electronic components with a high height.

If the height T ₂ of the electronic components is set to be lower than the thickness T ₁ of the sealing material (T ₁ > T ₂ ), and the surface where the unevenness of the electronic components is buried by the sealing material is set to be slightly smooth, even a plurality of electronic components with different heights Since the surface of the electronic substrate is smooth, it can not only isolate and seal the electronic components from the outside air, but also maintain them stably. In addition, if the height T ₂ of the electronic component is set higher than the thickness T ₁ of the sealing material (T ₁ ≦ T ₂ ), and the sealing material is closely connected along the outer surface of the electronic component, even if there are electronic substrates with multiple electronic components of different heights, the sealing The material covers at least the sides, thereby stably holding the electronic components. [Example]

The invention is illustrated on the basis of examples. Next, samples 1 to 26 described in the institute were produced, and various tests were performed.

＜Sample making＞

The sealing material composition and sealing material of Sample 1 were produced. Specifically, liquid epoxy resin with a flexible skeleton ("EP-4000S" manufactured by ADEKA Co., Ltd.) (hereinafter referred to as "epoxy resin 1") (hereinafter referred to as "epoxy resin 1") 41.3 mass Parts, modified aliphatic polyamine of polyamine ("EH-4357S" manufactured by ADEKA Co., Ltd.) (hereinafter referred to as "polyamine 1") 15.9 parts by mass, liquid diene rubber with carboxyl group and methacryl Base liquid polyisoprene rubber (30Pa‧s, 38°C, molecular weight 17000, number of functional groups carboxyl group: 2, methacryl group: 2) (hereinafter referred to as "liquid diene rubber 1") 42.8 mass parts and 1.3 parts by mass of 1-hydroxycyclohexyl phenone as a photopolymerization initiator were mixed to obtain a uniform liquid composition.

Next, the liquid composition was heated at 120° C. for 60 minutes in a state sandwiched between a pair of peeling films so that the thickness of the composition was 1.0 mm, and the epoxy compound having two or more epoxy groups, etc. reaction to prepare a sheet-shaped sealing material composition, which was used as the sealing material composition of Sample 1.

Then, the peeling film on one side of the sealant composition was peeled off, and an epoxy resin substrate with a thickness of 1 mm was stuck on the exposed surface of the sealant composition, and then pressed with a pressure of 0.3 MPa for 5 seconds using a flat pressing plate. Then, ultraviolet rays were irradiated under the conditions of intensity 600 mW/cm ² and integrated luminous flux 5000 mJ/cm ² to prepare a sealing material, which was used as the sealing material of Sample 1.

The sealing material compositions and sealing materials of related samples 2 to 26 were produced under the same conditions except that the raw materials and formulations of sample 1 were changed to the raw materials and blending amounts shown in the table. In addition, regarding the formulation of each sample, the mass parts of each raw material are described with the total of the epoxy compound having two or more epoxy groups, the polyamine, and the liquid diene rubber being 100 mass parts.

[Table 1]

[Table 2]

[table 3]

[Table 4]

Each raw material system shown in the table is as follows. Epoxy resin 2: bisphenol F type epoxy resin (DIC Co., Ltd. "EPICLON EXA-835LV") Epoxy resin 3: Liquid epoxy resin with two or more epoxy groups and a flexible skeleton (DIC Co., Ltd. "EXA-4850-150") Polyamine 2: epoxy amine adduct (Ajinomoto Fine-Techno Co., Ltd. "Amicure MY-24") Liquid diene rubber 2: Liquid polyisoprene rubber (70Pa‧s, 38°C, molecular weight 28000, no functional group ) Liquid diene rubber 3: liquid polyisoprene rubber without (meth)acryl group but with acid anhydride group (200Pa‧s, 38℃, molecular weight 34000, functional group number 3=acid anhydride group number 3) Liquid diene rubber 4: liquid polyisoprene rubber with no (meth)acryl group but carboxyl group (430Pa‧s, 38℃, molecular weight 30000, functional group number 10=carboxyl group number 10) Liquid diene rubber 5: Liquid polybutadiene rubber with methacryl groups but no epoxy-reactive groups (100 Pa‧s, 38°C, molecular weight 4000, functional group number 2=methacryl aryl acryl radical 2)

＜Test method and test result＞

The sealing material composition and sealing material of each of the above-mentioned samples were tested from various viewpoints shown below, and observed and evaluated.

(1) The shapeability of the sealing material composition:

Regarding the setting property, the sealant composition formed by coating the liquid composition on the release film and hardening can be evaluated from the state of the sealant composition when the release film is torn off. Here, the sealant composition that could be peeled while maintaining its shape was rated as "○", and the one that could be peeled but deformed such as elongation was rated as "△". On the other hand, those whose sealant composition flowed out from the release film without being solidified, and those whose cohesive force was extremely weak and whose sealant composition was difficult to peel from the release film were rated as "╳". Those with "○" or "△" can be evaluated as being usable as a sealing material composition, including shape fixability. On the other hand, those with "╳" are difficult to stick within the predetermined range of the sealed object, and there is a possibility of flowing out of the predetermined range, so they are not stereotyped. The evaluation results of the sealing material compositions of related samples 1~26 are shown in the table.

(2) Storage elastic modulus of the sealing material composition:

Cut the sealing material composition into a size of 5.0 mm wide x 30.0 mm long (thickness 1.0 mm), and prepare a test piece for measurement. Use a dynamic viscoelasticity measuring device ("DMS6100" manufactured by Seiko Instruments Co., Ltd.) to measure the distance between the clamps 8mm, frequency 1Hz, tensile mode to measure storage elastic modulus E'. The temperature characteristics of the sealing material composition can be evaluated by performing measurements under three conditions of measurement temperatures of 23°C, 60°C, and 120°C. The storage elastic modulus measured according to the above conditions is preferably in the range of 0.1~0.6MPa. The storage elastic modulus values of the sealing material compositions of related samples 1-26 are shown in the table.

(3) Adhesiveness of the sealing material composition:

After adhering the sealing material composition on a substrate with a height of 25% of the thickness of the sealing material composition and making it tightly bonded, the adhesiveness that includes no gaps for 30 seconds is rated as "○", and the ones that do not have Those with such adhesiveness were rated as "╳". The relevant evaluation results are shown in the table.

(4) Gel fraction of the sealing material composition:

A sealant composition with a predetermined weight W1 was left in toluene at room temperature for 24 hours, then the sealant composition not dissolved in toluene was taken out, and the weight W2 after evaporating toluene contained in the sealant composition was measured. The ratio of the weight W2 of the toluene-insoluble component to the initial weight W1 of the sealing material composition is defined as a "gel fraction".

Gel fraction (%)=W2/W1×100 W1: Weight of the sealant composition before the test W2: Weight of the sealant composition after the test

Among the components contained in the sealing material composition, the insoluble components include, for example, three-dimensional crosslinked epoxy resin hardened body and reaction products. On the other hand, the components dissolved in toluene, in addition to epoxy compounds with two or more epoxy groups, polyamines, and liquid diene rubbers, can still react, for example, with weaker interactions. Products, reaction products without three-dimensional cross-linking (hereinafter referred to as "dissolution reaction products"). Therefore, when the gel fraction is small, the sealing material composition contains at least any of epoxy compounds having two or more epoxy groups, polyamines, liquid diene rubber, and elutionable reaction products. one. Also, it was found that such eluted substances did not remain when the gel fraction was 100%.

However, the above-mentioned gel fraction is reduced in the sealant composition composed of polyamine and liquid diene rubber. This phenomenon can be considered that the reaction product of the polyamine and the liquid diene rubber is formed by utilizing a weak interaction, or a reaction product that does not have a sufficient three-dimensional structure that can maintain the structure in toluene , and solidification occurs. Here, if the functional group system considers the interaction between the amine group of the polyamine and the carboxyl group of the liquid diene rubber, it can be predicted that the effect of the acid-base interaction will be exerted. On the other hand, when the amine group of the polyamine reacts with the (meth)acryl group of the liquid diene rubber, it is considered that a reaction product is formed by a covalent bond. The gel fraction (%) of the sealing material composition of related samples 1~26 is shown in the table.

(5) Mechanical strength (tensile test) of the sealing material composition:

For the mechanical strength of the related sealing material composition, the maximum tensile stress (also called "tensile strength"), elongation at break (also called "tensile elongation at break"), and 100% elongation were measured according to JIS K 6251 stress. First, the sheet-shaped sealing material composition was cut into a No. 1 dumbbell shape using a hollow die, and two marking lines were drawn at intervals of 10 mm on the rod-shaped portion of the dumbbell-shaped sample. Next, a tensile force is applied to both ends of the sample under certain conditions, and the maximum tensile force until the sample breaks and the elongation between the marked lines are measured. Also, the tensile force when the marked lines were extended by 100% (that is, the state between the marked lines was twice the initial state) was measured. Then, the maximum tensile stress, elongation at cutting, and 100% elongation tensile stress were calculated using the following formula (1), formula (2), and formula (3), respectively. The equivalents are shown in the table.

TS=F _m /S‧‧‧Formula (1) E _b =(L ₁ -L ₀ )/L ₀ ×100‧‧‧Formula (2) TS ₁₀₀ =F ₁₀₀ /S‧‧‧Formula (3)

TS: maximum tensile stress (MPa) F _m : maximum tensile force (N) S: initial cross-sectional area of the test piece (mm ² ) E _b : elongation at break (%) L ₀ : distance between initial marking lines ( mm) L ₁ : Distance between marking lines at break (mm) TS ₁₀₀ : Tensile stress at 100% elongation (MPa) F ₁₀₀ : Tensile force at 100% elongation (N)

(6) Hardening of sealing material (storage modulus of elasticity):

Regarding the degree of hardening of the sealing material formed by irradiating the sealing material composition with light, since the hardness changes along with the hardening, the degree of hardening is evaluated by the change in the storage elastic modulus. The measurement of the storage elastic modulus E' is to cut the sealing material into a size of 5.0 mm wide x 30.0 mm long (thickness 1.0 mm), and prepare a test piece for measurement, using a dynamic viscoelasticity measuring device (manufactured by Seiko Instruments Co., Ltd. DMS6100"), the distance between fixtures is 8mm, the frequency is 1Hz, the measurement temperature is 23°C, and the tensile mode is implemented. The storage elastic modulus means that when about 0.01-0.60 MPa is applied to the sealing material composition, the storage elastic modulus of the sealing material is in the range of 0.5-10 MPa, and the change rate of the storage elastic modulus at this time is at least 200%. Therefore, the change rate of the storage elastic modulus was 200% or more as "○", and the change rate of 200% or less was "╳". The evaluation results and the change in storage elastic modulus before and after the sealing material composition is hardened into a sealing material are shown in the table.

Another evaluation method of hardening is that for the sealant composition with adhesiveness on the surface, it can be judged from the disappearance of adhesive force that the liquid diene rubber showing adhesive force has reacted and fully hardened.

(7) Waterproofness of sealing material (water immersion test):

The water resistance of related sealing materials is evaluated by the test of IPX7 standard stipulated in JIS C0920. Specifically, a 5 mm × 5 mm water immersion detection sealing strip was pasted on an epoxy resin substrate with a thickness of 1 mm, and after the 10 mm × 10 mm × 1 mm sealing material composition was pasted in such a way as to cover the water immersion detection sealing strip, by irradiating ultraviolet rays , and the test piece of the water immersion detection sealing strip covered by the sealing material on the epoxy resin substrate was produced. The test piece was placed under the water depth of 1m for 30 minutes in a static state, and then it was taken out, and evaluated according to whether water was detected on the sealing strip by water immersion. The case where water was not detected was rated as "○", and the case where water was detected was rated as "╳". The evaluation results are shown in the table.

(8) Adhesion of sealing material:

Although the sealing material does not necessarily have to have a strong adhesive force, it must include an adhesive force that does not impair the waterproofness. Here, after confirming the bonding state after the above IPX7 test, the case where the sealing material was still attached after the test was rated as "○", and the case where the sealing material peeled off after the test was rated as "╳". The evaluation results are shown in the table.

(9) Water vapor permeability of sealing material:

The sealing material is preferably able to block not only liquid water, but also gaseous water (ie, water vapor). The water vapor permeability can be evaluated by the cup method stipulated in JIS Z0208, and the water vapor permeability is preferably 50g/m ² ‧24h or less. In this water vapor permeability test, a test piece made of a sealing material with a thickness of 1mm was produced, and the water vapor permeability was measured under the conditions of 40°C and 90%RH. The measured values are shown in the table.

＜Survey＞

Samples 1 to 6 are samples in which the ratio of the epoxy resin 1 to the polyamine 1 is a constant total mass, and the mass ratio to the liquid diene rubber 1 is changed. From these samples, the settability of samples 1 to 4 is excellent, but the settability of sample 5 is still within the usable range, but slightly poor. The reason is considered to be that the rate of unreacted liquid diene rubber in the sealant composition increases, and the crosslink density of the reaction product decreases, resulting in poor settability. From this point of view, it can be seen that the ratio of the liquid diene rubber to the total amount of epoxy compounds having two or more epoxy groups, polyamines, and liquid diene rubber is 95.3% by mass or less. The settability of the degree of use is good if it is 94.2% by mass or less. On the other hand, in sample 6, which has a relatively small liquid diene rubber ratio of 35.0% by mass, when an epoxy compound having two or more epoxy groups, a polyamine, and a liquid diene rubber are mixed, no Uniform liquid composition, after heating, part of the components will flow out in liquid state, and the shape setting is rated as "╳". Therefore, liquid diene rubber is compared to epoxy compounds with more than 2 epoxy groups, The total ratio of the polyamine and the liquid diene rubber must exceed 35% by mass, and it was confirmed from the results of Sample 1 that if the content is 42.8% by mass or more, excellent settability can be achieved.

Related samples 1-5 belong to the sealing material composition with a storage elastic modulus of 0.004-0.75 at 23°C, excellent flexibility, and adhesiveness on the surface. Here, it was found that the storage elastic modulus tends to decrease as the ratio of the liquid diene rubber increases. In addition, almost no temperature dependence of the storage elastic modulus was found in the related samples, and even when heating was applied, there was no elution.

Furthermore, the gel fractions of the sealing material compositions of samples 1-5 are in the range of 69.2-79.7%. In the measurement of the gel fraction, since the unreacted liquid diene rubber dissolves in toluene, it is suggested that there is a component that reacts and becomes insoluble in toluene. From the above gel fraction, it is suggested that more than half of the liquid diene rubber blended will form some kind of reaction product, and from the temperature dependence of the storage elastic modulus, it is suggested that the epoxy group of the epoxy compound, and the The carboxyl groups of the liquid diene rubber react to form a reaction product.

The elongation of the sealing material compositions of samples 1-5 is 186-512% when cut, and they are easy to elongate and not easy to break. In particular, when the proportion of liquid diene rubber is 50.0~94.2%, the elongation at cutting is more than 200%, and the maximum tensile stress is more than 0.1MPa, so the stress at elongation and the difficulty of crushing are excellent in balance.

Regarding samples 1 to 5, each sealing material composition was excellent in photocurability. The storage elastic modulus of the hardened sealing material is 0.8~5.4MPa. Among them, those with a liquid diene-based rubber proportion of 50.0% or more have a storage elastic modulus of 4 MPa or less, and form a soft sealing material. In addition, the storage elastic modulus of the liquid diene-based rubber ratio of 88.9% or less is 1 MPa or more, and it is known that a certain degree of rigidity is included. In addition, the results of the water immersion test of each sample were good, and they had predetermined adhesive force. In addition, the water vapor permeability of any of them was 20 g/m ² ·24h or less, and it was found that the predetermined low moisture permeability was included.

Sample 7 was not blended with liquid diene-based rubber, and was cured by heating, and was extremely hard, and a hardened product lacking in flexibility was obtained. Related to this sample 7, there is no adhesiveness or photocurability.

Sample 8 was not blended with an epoxy compound having two or more epoxy groups and a polyamine, and it was not possible to obtain a shape-fixing sealing material composition. Therefore, tests related to the sealing material composition could not be carried out. On the other hand, it is solid after being irradiated with ultraviolet rays, and related tests on sealing materials can be carried out.

Sample 9 and sample 10 are the samples which changed the compounding quantity of the epoxy compound which has 2 or more epoxy groups, and polyamine. Samples 1 to 6 are blended with epoxy compounds having more than two epoxy groups and polyamines in such a way that epoxy equivalents and active hydrogen equivalents become 1:1, while sample 9 is blended with The epoxy compound having two or more epoxy groups was excessively blended, and the sample 10 was excessively blended with polyamine. Sample 9 and Sample 10 both have predetermined properties as a sealing material composition and a sealing material.

Sample 11 is an epoxy compound having two or more epoxy groups using bisphenol F epoxy resin without a flexible skeleton. Related sample 11 also obtained almost the same test results as samples 3 and 4. It is known that when the proportion of liquid diene rubber is high, even if the type of epoxy compound with two or more epoxy groups is changed, the A sealant composition and a sealant with similar properties are obtained.

Sample 12 and Sample 13 are characteristic samples not blended with polyamine. That is, a liquid composition mainly composed of an epoxy compound having two or more epoxy groups and a liquid diene rubber is prepared, and heated to form a sample of a sealant composition.

The sealing material compositions of Sample 12 and Sample 13 both had shape fixability. It can be seen from this that epoxy compounds with more than two epoxy groups do not necessarily react with polyamines and epoxy resin hardeners to form a matrix. Utilizing epoxy compounds with more than two epoxy groups and liquid The reaction product of diene rubber can also be cured to impart setability. In addition, this phenomenon suggests that the test results of the samples described later are caused by the reaction between the epoxy group of the epoxy compound and the carboxyl group of the liquid diene rubber.

The sealing material compositions of Sample 12 and Sample 13 all have the same properties as Samples 3 and 4, and the temperature dependence of the storage elastic modulus is also small. The sealing materials of related samples 12 and 13 also have the same properties as samples 3 and 4, and it can be seen that a predetermined sealing material composition and sealing material can be obtained even without the addition of polyamine.

Sample 14 and Sample 15 are characteristic samples that are not blended with an epoxy compound having two or more epoxy groups. That is, a liquid composition mainly composed of a polyamine and a liquid diene rubber was prepared, and then heated to form a sample of a sealing material composition. Both sample 14 and sample 15 have shape fixability. From this, it can be seen that even if the epoxy compound having two or more epoxy groups is not contained, the reaction product of the polyamine and the liquid diene rubber is used for curing, including the settability.

Although the sealing material compositions of Sample 14 and Sample 15 had a large storage elastic modulus at 23° C., unlike the previous samples, it was found that the temperature dependence of the storage elastic modulus was large. That is, the storage elastic modulus is greatly reduced by heating. Specifically, the storage modulus of elasticity at 60°C is 4.3% for sample 14 and 41% for sample 15 compared to that at 23°C. In addition, the storage modulus of elasticity at 120°C was not calculated compared to that at 23°C (at least 4.3%) for sample 14, and 5.1% for sample 15. This kind of sample is better in terms of tracking finer unevenness by heating. This phenomenon implies that in addition to the three-dimensional cross-linking structure, the polyamine and the liquid diene rubber may form a reaction product utilizing the weak bond interaction that is affected by toluene. This kind of reaction can be regarded as the acid-base interaction between carboxyl group and amine group, and the reaction between (meth)acryl group and amine group. In addition, concerning sample 14 and sample 15, the gel fraction of sample 14 is 0%, and the gel fraction of sample 15 is 82%, and there is a large difference, and both samples show the result that the temperature dependence of the storage elastic modulus is large . Therefore, it is known that when the polyamine is used as the main compound, the obtained sealing material composition is not affected by the gel fraction, and the storage elastic modulus can be greatly reduced by heating.

On the other hand, although the water vapor transmission rate of the sealing materials related to the above-mentioned samples 14 and 15 is slightly higher, they have the same properties as the samples 3 and 4. In the case of epoxy compounds, the properties of the sealing material will not change much.

Samples 16 to 19 are samples in which the type of liquid diene rubber is changed. Specifically, sample 16 used a liquid diene rubber not having a functional group. Sample 17 used a liquid diene rubber having an acid anhydride group but no (meth)acryl group. Sample 18 uses a liquid diene rubber that has a carboxyl group but does not have a (meth)acryl group. As sample 19, a liquid diene rubber having no carboxyl group but having a (meth)acryl group was used.

Regarding these samples, when focusing on the shape fixability of the sealing material composition, sample 18 is "◯" and sample 17 is "△". On the other hand, the setting properties of the remaining samples were "╳". From this phenomenon, it can be seen that the carboxyl group plays a large role in order to include the fixity. Also, it was found that if the carboxyl group forms an anhydrate, the effect of improving the settability will be greatly reduced, but the effect of imparting the settability still slightly remains even in the case of an anhydrate compound.

On the other hand, when looking at the photocurability of the sealing material, the photocurability of sample 19 having a (meth)acryl group is "○", while the other samples have no photocurability.

From the above evaluation results, it can be seen that the liquid diene rubber must contain both carboxyl groups and (meth)acryl groups.

Samples 20 to 22 are the same as samples 12 and 13, except that polyamine is not blended, and the blending amount of epoxy resin and liquid diene rubber is changed, and all of them have shape fixability. However, since the settability of sample 22 was "△", it was found that the ratio of the liquid diene rubber is preferably less than 96.2.

In addition to samples 12, 13, 20~22, samples 23 and 24 are also blended with functional groups (carboxyl, acid anhydride, hydroxyl) that do not contain (meth)acryl groups but that can react with epoxy groups. etc.) of diene rubber. The sealing material compositions of Sample 23 and Sample 24 have a breaking elongation of 200% or more and a maximum tensile stress of 0.2 MPa or more, so it is known that the handling property is very good, and fracture due to elongation is less likely to occur. In addition, the sealing materials related to the samples 23 and 24 were also excellent in both flexibility and stretchability.

Samples 25 and 26 are samples using liquid polyisoprene rubber with carboxyl groups and liquid polybutadiene rubber with methacryl groups. The result of the test is "○".

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Claims (17)

A sealing material composition, which has shape-setting properties, and contains: a reaction product of an epoxy compound having two or more epoxy groups and a polyamine; A reaction product of an acryl-based liquid diene rubber and an epoxy compound having two or more epoxy groups; and a photopolymerization initiator wherein, compared to the above-mentioned epoxy compound having two or more epoxy groups A total of 100 parts by mass of the compound and the above polyamine contains 100 to 2000 parts by mass of the liquid diene rubber. For example, the sealing material composition of item 1 of the scope of the patent application has shape-setting properties, wherein the above-mentioned epoxy group is a reactive group and is a carboxyl group; and contains: an epoxy compound with more than 2 epoxy groups, and a polyamine The reaction product; the reaction product of a liquid diene rubber with (meth)acryl group and carboxyl group, and an epoxy compound with more than 2 epoxy groups; and a photopolymerization initiator; it also includes It is a reaction product of liquid diene rubber with (meth)acryl and carboxyl groups and polyamines. A mixture forming the sealing material composition as described in Item 1 of the scope of the patent application, which contains: an epoxy compound with more than two epoxy groups, a polyamine, a group reactive to epoxy groups and (methyl ) a mixture of acryl-based liquid diene rubber and a liquid composition of a photopolymerization initiator, wherein 100% by mass of the total of the above-mentioned epoxy compound having two or more epoxy groups and the above-mentioned polyamine parts, containing 100 to 2000 parts by mass of the liquid diene rubber. A sealing material composition having shape-setting properties, comprising: an epoxy compound having two or more epoxy groups, and a liquid diene system having a reactive group to epoxy groups and a (meth)acryl group A reaction product of rubber; and a photopolymerization initiator, but not containing a polyamine, wherein the above-mentioned liquid diene system is contained with respect to 100 parts by mass of the above-mentioned epoxy compound having two or more epoxy groups 100-2600 parts by mass of rubber. Such as the sealing material composition of item 4 of the patent scope of the application, wherein the above-mentioned epoxy group belongs to The reactive group is a carboxyl group. A mixture forming the sealing material composition as described in item 4 of the scope of the patent application, which contains: an epoxy compound with more than 2 epoxy groups, a reactive group to epoxy groups and (meth)acrylic Acyl-based liquid diene rubber and a photopolymerization initiator, but a liquid composition mixture containing no polyamine, wherein, relative to 100 parts by mass of the above-mentioned epoxy compound having two or more epoxy groups, 100-2600 parts by mass of the liquid diene rubber. Such as the mixture of claim 3 or 6, wherein the above-mentioned liquid composition further contains a hardener for epoxy resin other than polyamine. Such as the sealing material composition of claim 1 or 4, which further contains a liquid diene rubber that does not have a (meth)acryl group but has a reactive group to an epoxy group. Such as the sealing material composition of item 1 or 4 of the scope of the patent application, wherein the liquid diene rubber with reactive groups to epoxy groups and (meth)acryl groups has (meth)acryl groups The first liquid diene rubber that has no reactive groups to epoxy groups, and the second liquid diolefin rubber that has reactive groups to epoxy groups but no (meth)acryl groups. Mixture of ethylenic rubber. A sealing material composition having shape-setting properties, comprising: a reaction product of a liquid diene rubber with a (meth)acryl group and a carboxyl group and a polyamine, and a photopolymerization initiator, but does not contain 2 A reaction product of an epoxy compound having more than one epoxy group, which contains 100 to 2,000 parts by mass of the liquid diene rubber relative to 100 parts by mass of the polyamine. A mixture forming the sealing material composition as described in item 10 of the scope of the patent application, which contains: polyamine, liquid diene rubber with (meth)acryl and carboxyl groups, and a photopolymerization initiator, However, a mixture of a liquid composition not containing an epoxy compound having two or more epoxy groups, wherein 100 to 2000 parts by mass of the liquid diene rubber is contained relative to 100 parts by mass of the above-mentioned polyamine. A sealing material, which is a light-hardening body of the sealing material composition in item 1, 4 or 10 of the patent scope. Such as the sealing material in item 12 of the scope of patent application, wherein the storage modulus of elasticity is 0.7~5.4MPa. An electronic substrate is used to seal the electronic components by using the sealing material in item 12 of the scope of the patent application. For example, the electronic substrate of claim 14, wherein the height T ₂ of the above-mentioned electronic component is relative to the thickness T ₁ of the sealing material, T ₁ > T ₂ , and the surface of the sealing material embedding the unevenness of the above-mentioned electronic component is slightly smooth. The electronic substrate according to claim 14, wherein the height T ₂ of the electronic component relative to the thickness T ₁ of the sealing material is T ₁ ≦ T ₂ , and the sealing material is in close contact with the outer surface of the electronic component. For example, the electronic substrate of the 14th patent scope of the application includes a flexible base material with a storage elastic modulus of 0.7~50MPa.